Thionaphthene-indole condensation vat dyestuffs



Patented Sept. 5, 1933 UNITED STATES PATENT OFFIC THIONAPHTHENE-INDOLEOONDENSATION VAT DYESTUFFS Karl Thiess and Theodor Meissner,Frankforton-the-Main-Hoehst,

fort on the Main Runne, Frankfort Werner Zerweek, Frank- Feohenheim, andErnst on the Main Hochst,

Germany, assignors to General Aniline Works, Inc., New York, N. Y., acorporation of Delaware No Drawing. Application April 5, 1929, SerialNo. 352,910, and in Germany April *7, 1928 Claims.

wherein Y1 stands for hydrogen, halogen or an alkyl group, at least oneY1 being halogen or alkyl, Y2 for hydrogen, halogen or an alkoxy group,one Y2 at least being an alkoxy group and R for halogen or an arylideresidue, with a hydroxythionaphthene compound which may be substitutedin the benzene nucleus by halogen or alkyl.

The. condensation may be carried out by causing the components to actupon one another in the presence of a solvent such as chlorobenzene,benzene, nitrobenzene or the like. When using as the starting material asubstituted alkoxyisatin-a-arylide one may also use as the diluentalcohol, acetic anhydride or water. If required the reaction may beaccelerated by moderately heating the mass.

The dyestuffs thus obtainable are compounds of the following generalformula:

X 0 I ll I f-5 methyl-'I-methoxyisatin are transformed into thecorresponding isatin-u-chloride by heating them with 22 parts ofphosphorus pentachloride in 200 parts of chlorobenzene. After the twosolutions have been combined, 5-chloro-7-methyl-(2) thionaphthene-4-methyl -'7' methoxy (2) indolindigo immediately separates in acrystalline form. After the product has been heated for a short time toabout from 80 C. to 90 C. in order to complete the formation of thedyestuff, the 5- chloro -7- methyl-(2) -thionaphthene- 4'-methyl-T-methoxy-(2')indolindigo is filtered cold by suction and washed withalcohol for the purpose of removing the chlorobenzene.

The reaction may be illustrated by the following equation:

21H; Ill 30H:

The dyestuff thus obtained dyes the fiber from a yellow vat dullgreenish-blue tints.

(2) If in Example 1 the 4-methyl-7-methoxyisatin is replaced by 22.6parts of 4-methyl-5- chloro-l-methoxy-isatin and the further operationsare .carried out as described in Example 1,5-chloro-7-methyl-(2)-thionaphthene-4- methyl-5'-chlor-7'-methoxy-(2')-indolindigo is obtained. This dyestufi dyes the fiber from a goldenyellow vat marine-blue tints of good fastness to Washing, boiling andchlorine.

(3) 22.6 parts of 4-methyl-5-ohloro-7-methoxyisatin are transformed intothe corresponding isatin-u-chloride by heating it with 22 parts ofphosphorus pentachloride in 200 parts of chlorobenzene and introducedinto a solution of 21.3 parts of 4.7-dimethyl-5-chloro-3-hydroxy-1-thionaphthene in 200 parts of 'chlorobenzene. The new dyestuff whichseparates from the solution is filtered and freed from the chlorobenzeneby washing it with alcohol. The 4.7-dimethyl- 5-ch1or- (2)-t11ionaphthene- 4-methy1 -5- chlor- I'-methoXy-(2')-indolindigo dyesthefiber from a golden-yellow vat blue tints of good fastness towashing, boiling and chlorine.

- of -thedyestuff of :Example 4.

(Gr-By substituting in Example 3.18.5 parts- (4) By substituting inExample 3, 23.3 parts of 4-methyl-5.7-dichlor-3-hydroxy1-thionaphthenefor the 4.7-dimethyl--chlor3-hydroxy-1- thionaphthene and performing thefurther working-process according to Example 3, il-methyl- 5.7- dichlor-(2) thionaphthene 4' methyl-5' is. obtained. This dyestuff dyes thefiber'from a"yellow'olive chlor-Z -methoxy- (2 -indolindigo vat clearblue tints of good fastness to washing, boiling and chlorine. Thetintismore greenish than that of the dyestuffs obtained according toExamples 2 and 3. i

(5) By substituting in Example 319.9 parts of5-methyl-'7-chlor-3-hydroxy-I-thiOnaphthene I4.7-dimethyl-5-chlor-3hydroxythiofor the naphthene and further workingin the same man ner as in Example 3, the 5-methyl-'i-chlor-(2)thionaphthene-4' methyl-5' chlor -7"- methoxy- (2') -indolindigo isobtained which dyesthe fiber from a yellow vat a tint which is similarto that i l of 5-chlor-3-hydroxy-l thionaphthene for #the 4.7- dimethyl-5- chlor -3- hydroxy -lthionaphthene and otherwise working in the samemanner as indicated in this exampl'e 5-chlor-2-thionaph-- 1 thene-4methyl -5'-' chler-'Z-methoxy-(2) -in--- dolindigo is obtained; Thisdyestufi dyes-tho fiber froma yellow vat blue tints of good fastnessproperties;-L-Itsshade is somewhat greener. than i that of-th'e':dyestuff prepared according to Example 3. i

(7) 21.2 parts .oi: .5-methoxy-7 chlor isatin "dissolved in 200-partsofchlorobenzene aretransisatin-chloride byheat-ing it in about 250 partsof' chlorobenzene with 24 parts of phosphorus pentachloride. Thissolution is poured into another solution of 25 partsof-"'5.6.7-trichloro-3-hydroxy- 1-thionaphthene in 250 parts ofchlorobenzenei and heating is continued for some time on the waterbathuntilthe condensation is complete.

hol and dried. Thus a: violet-bluepowder is obtained which dissolves inconcentrated'sur- .furic acid-to a bluish-greensolution. and; dyes icotton from a reddish-yellow .vati blue tints of 1 very good fastnessproperties.

qchloride by'means of 24 parts of phosphorus 'pentachloride dissolved in220 parts of chloro- (9) 22 parts of 4-chlor-l-methoxy-isatin aretransformed into the corresponding-:isatin-abenzene. Then a solution of.22 parts of 5.7- dichloro-3shydroxy-l-thionaphthene in 220 parts ofchlorobenzene is added and the mixture is The. dyestuff' separating in'a crystalline form is filtered byrsuction, washed with chlorobenzeneand'alcohol and dried. The violet-bluepowder.

thusobtained dissolves in'concentrated sulfuric 1 tints.

' more reddish-blue ;tints.

'trated surfuric acid to a bluish-green solution (10) A solution ofeohior-rz-meihox sisatin-si.

chloride, prepared as described in Example 9, is condensed with 23 partsof 4'-methyl-5.7-dichlor- 3-hydroxy-'l-thionaphthene dissolved..- in 200parts of chlorobenzene according to the proc-- esses described in thepreceding examples. The dyestufi thus obtained forms a violet-bluepowder which dissolves inconcentrated surfuric acid to a greenish-bluesolution. It dyes the fiber from a reddish-yellow vat fast marine-bluetints.

(11) When using in Example 10 instead of 4- methyl 5.7.dichlor-3-hydroxy 1 thionaphthene the corresponding'quantity of 4.7-dimethyl-5-chlor-3-hydroxy-1-thionaphthene, 4.7-dimethyl- 5chloro-2-thionaphthene4-chloro-7-methoxy- 2-indolindigo isbobtainedwhich is very similar to that of example 10 but which dyes the fiber Itdissolves in concenand-yields a yellow vat.

(12) When substituting in Example 10 25 parts of.5.6.7-trichloro-3-hydroxy-l-thionaphthene fore-methyl-hfl-dichlor-S-hydroxy-l-thionaphthene and otherwise Working inthesame -rnanner as indicated in this example a dyestuif is obtainedwhich dissolves in concentrated sulfuric acidto 150 a bluish-greensolution. Its hydrosulfite vat has an'orange-yellow coloration;- It dyescottonpureblue tints which have a more greenish hue than that of thedyestuff of Example 10.

(13) 22 parts of i-chloro-7-methoxy-isatin are transformed into thecorresponding isatin-ochloride by heating with 24 parts of phosphoruspentachloride in 220 parts of chlorcbenzene. The solution thus obtainedis added to a solution of 18.5 parts of5-chloro-3hydroxy-1-thionaphthene in 200 parts of chlorobenzene. The.formationofthej dyestuff is completed by. moderately heating onthewater bath. After cooling, the dyestuff "whichhas separated'in theform "ofbluish -violet crystals isfiltered by suction washed withchlorobenzene and alcohol .alnd dried. It dissolves in. concentratedsulfuric acid to a' greenish-blue solution and dyes cottonfrom a yellowhydrosu'lfite vat beautiful marine-blue tints. W 'f (14) 22. partsof-'5.7 dichloro-'3rliydroxy-1-- 'thionaphthene are'dissolved,'whileboiling, in 18G parts of chlo'robenzene and Jfiltered. The

filtered solution is introduced while stirring at from 40 C. to 50 G.into asolution'of 4-methyl 5--chlo1o-7-metliodxy-isatin-d chlorideprepared from 22.6 parts of-this isatin derivative ,as' described inExample 8. After a short boiling, the condensation is completef Theseparated dyestulf is filtered by suction and washed with chlorobenzeneand-\alcohol. It dissolves in anhydrous sulfuricacid'to argreenish-bluesolution, in hot nitrobenzene to a bright-blue solution. Cotton and woolare dyed from the alkaline hydrosulfite vat pure-blue tints. Thedyeing's are of a more greenish shade than that of the dyestuff' ofExample 2.

15) By substituting: in Example 14:30.8rparts of 5.7-dibromo-3hydroxyl-thionapthene for 5.7 dichloro3 hydroxy-'I-thionaphthene. a dyestuff= is obtained which-yields somewhatzzmore heated for some furthertime-on the water bath.

- droxy-l-.thionaphthene are. dissolved while :boiling; 180'.-*pa-rtsof: :chlorobenzene 'andvfiltered.

The filtered solution is introduced while stirring at from C. to C. intoa solution of l-methyl- 5-chloro-7-ethoxy isatin oz chloride preparedfrom 24 parts of the said isatin and 22 parts of phosphoruspentachloride in 200 parts of chlorobenzene. After a short heating thecondensation is complete. The separated dyestufi is filtered by suction,washed first with chlorobenzene and then with alcohol.

The 4:.7-dimethyl-5-chloro- (2) -thionaphthene 4'-methy1-5'-chloro-'7-ethoxy -(2) indolindigo dissolves in concentrated sulfuric acid to abluishgreen solution, in hot nitrobenzene to a brightblue one. It dyesthe fiber from an olive vat blue tints of good fastness properties. Theshade of the dyeings is more reddish than that of the dyestuff ofExample 14.

(18) 22 parts of 5.7-dichloro-3-hydroxy-1- thionaphthene are made into apaste with 400 parts of water and into this suspension are introducedwhile stirring at C. to C. 30 parts of 4- rnethyl-5-chloro -'7 methoXyisatin 0c anilide made into a paste with about 250 com. of water. Theformation of the dyestuff sets in at once while aniline is split off.Stirring is continued at from 60 C. to 70 C. until no4-Inetnyl-5-chloro- '7-methoXy-isatin-aani1ide can any longer bedetected; the mass is then filtered hot by suction, Washed first withwarm diluted caustic soda solution and then with hot water and finallythe filtration residue is dried. The dyestufi" is identical with thatdescribed in Example 14.

We claim:

1. As a new product, the compound of the following formula:

dissolving in concentrated sulfuric acid to a greenish-blue solution, inhot nitrobenzene to a bright-blue solution and dyeing cotton and woolfrom an alkaline hydrosulfite vat pure-blue tints.

2. As a new product, the compound of the following formula:

dyeing the fiber from a golden yellow vat navyblue tints of goodfastness to washing, boiling and chlorine.

3. As a new product, the compound of the following formula:

dyeing the fiber from a yellow vat clear blue tints.

I O O Xzg (LL R l X:s

| S H X4 Ya wherein X1 stands for hydrogen or methyl, X2 stands forchlorine, bromine or methyl, X3 stands for chlorine, bromine orhydrogen, X4 stands for chlorine, bromine, hydrogen or methyl, Y1 standsfor chlorine, bromine, methyl or hydrogen, Y2 stands for hydrogen,chlorine, bromine or alkoxy, Y3 stands for chlorine, bromine or alkoxyand wherein the nucleus R in any case contains one alkoxy group andfurther one methyl group or one halogen atom in the positions as definedherein, said dyestuffs yielding from a vat yellowblue to blue tints.

5. As new products, the compounds of the following general formula:

if I Xzr-[I-C cl o1 I s NH X4

